Fabrication of Core–Shell Nanotube Array for Artificial Photosynthesis Featuring an Ultrathin Composite Separation Membrane
Abstract
We report macroscale arrays of cobalt oxide-silica core-shell nanotubes with high aspect ratio and ultrathin walls of less than 20 nm have been fabricated. The silica shells feature embedded oligo-para(phenylenevinylene) molecules for charge transport across the insulating silica layer, which is tightly controlled by their electronic properties. The assembly is based on the use of a sacrificial Si nanorod array template combined with atomic layer deposition, covalent anchoring of organic wire molecules, and dry cryo-etching. High-resolution TEM imaging of samples prepared by microtome affords structural details of single core-shell nanotubes. The integrity of silica-embedded organic wire molecules exposed to atomic layer deposition, thermal treatment, and harsh etching procedures is demonstrated by grazing angle ATR FT-IR, FT-Raman, and XPS spectroscopy. The inorganic oxide-based core-shell nanotubes with ultrathin gas-impermeable, proton-conducting silica shells functionalized by molecular wires enable complete nanoscale photosynthetic units for CO2 reduction by H2O under membrane separation. Arrays of massive numbers of such core-shell nanotube units afford a design that extends the separation of the incompatible H2O oxidation and CO2 reduction catalysis environments across the continuum of length scales from nanometers to centimeters.
- Authors:
-
[1];
[1]
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry; University of California, Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
- OSTI Identifier:
- 1580206
- Grant/Contract Number:
- AC02-05CH11231; SC0004993
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Volume: 12; Journal Issue: 1; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; artificial photosynthesis; nanotube array; core-shell; ultrathin silica membrane; molecular wires
Citation Formats
Edri, Eran, Aloni, Shaul, and Frei, Heinz. Fabrication of Core–Shell Nanotube Array for Artificial Photosynthesis Featuring an Ultrathin Composite Separation Membrane. United States: N. p., 2018.
Web. doi:10.1021/acsnano.7b07125.
Edri, Eran, Aloni, Shaul, & Frei, Heinz. Fabrication of Core–Shell Nanotube Array for Artificial Photosynthesis Featuring an Ultrathin Composite Separation Membrane. United States. https://doi.org/10.1021/acsnano.7b07125
Edri, Eran, Aloni, Shaul, and Frei, Heinz. Tue .
"Fabrication of Core–Shell Nanotube Array for Artificial Photosynthesis Featuring an Ultrathin Composite Separation Membrane". United States. https://doi.org/10.1021/acsnano.7b07125. https://www.osti.gov/servlets/purl/1580206.
@article{osti_1580206,
title = {Fabrication of Core–Shell Nanotube Array for Artificial Photosynthesis Featuring an Ultrathin Composite Separation Membrane},
author = {Edri, Eran and Aloni, Shaul and Frei, Heinz},
abstractNote = {We report macroscale arrays of cobalt oxide-silica core-shell nanotubes with high aspect ratio and ultrathin walls of less than 20 nm have been fabricated. The silica shells feature embedded oligo-para(phenylenevinylene) molecules for charge transport across the insulating silica layer, which is tightly controlled by their electronic properties. The assembly is based on the use of a sacrificial Si nanorod array template combined with atomic layer deposition, covalent anchoring of organic wire molecules, and dry cryo-etching. High-resolution TEM imaging of samples prepared by microtome affords structural details of single core-shell nanotubes. The integrity of silica-embedded organic wire molecules exposed to atomic layer deposition, thermal treatment, and harsh etching procedures is demonstrated by grazing angle ATR FT-IR, FT-Raman, and XPS spectroscopy. The inorganic oxide-based core-shell nanotubes with ultrathin gas-impermeable, proton-conducting silica shells functionalized by molecular wires enable complete nanoscale photosynthetic units for CO2 reduction by H2O under membrane separation. Arrays of massive numbers of such core-shell nanotube units afford a design that extends the separation of the incompatible H2O oxidation and CO2 reduction catalysis environments across the continuum of length scales from nanometers to centimeters.},
doi = {10.1021/acsnano.7b07125},
journal = {ACS Nano},
number = 1,
volume = 12,
place = {United States},
year = {Tue Jan 02 00:00:00 EST 2018},
month = {Tue Jan 02 00:00:00 EST 2018}
}
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Works referenced in this record:
The Artificial Leaf
journal, January 2012
- Nocera, Daniel G.
- Accounts of Chemical Research, Vol. 45, Issue 5
Roll-to-Roll Anodization and Etching of Aluminum Foils for High-Throughput Surface Nanotexturing
journal, July 2011
- Lee, Min Hyung; Lim, Namsoo; Ruebusch, Daniel J.
- Nano Letters, Vol. 11, Issue 8
A Stabilized, Intrinsically Safe, 10% Efficient, Solar-Driven Water-Splitting Cell Incorporating Earth-Abundant Electrocatalysts with Steady-State pH Gradients and Product Separation Enabled by a Bipolar Membrane
journal, April 2016
- Sun, Ke; Liu, Rui; Chen, Yikai
- Advanced Energy Materials, Vol. 6, Issue 13
Directed Assembly of Cuprous Oxide Nanocatalyst for CO 2 Reduction Coupled to Heterobinuclear ZrOCo II Light Absorber in Mesoporous Silica
journal, August 2015
- Kim, Wooyul; Frei, Heinz
- ACS Catalysis, Vol. 5, Issue 9
TiO2 Nanotubes: Synthesis and Applications
journal, March 2011
- Roy, Poulomi; Berger, Steffen; Schmuki, Patrik
- Angewandte Chemie International Edition, Vol. 50, Issue 13
A monolithic device for CO 2 photoreduction to generate liquid organic substances in a single-compartment reactor
journal, January 2015
- Arai, Takeo; Sato, Shunsuke; Morikawa, Takeshi
- Energy & Environmental Science, Vol. 8, Issue 7
Solar-Driven Reduction of 1 atm of CO 2 to Formate at 10% Energy-Conversion Efficiency by Use of a TiO 2 -Protected III–V Tandem Photoanode in Conjunction with a Bipolar Membrane and a Pd/C Cathode
journal, September 2016
- Zhou, Xinghao; Liu, Rui; Sun, Ke
- ACS Energy Letters, Vol. 1, Issue 4
Assembly of one dimensional inorganic nanostructures into functional 2D and 3D architectures. Synthesis, arrangement and functionality
journal, January 2012
- Joshi, Ravi K.; Schneider, Jörg J.
- Chemical Society Reviews, Vol. 41, Issue 15
Inorganic core–shell assemblies for closing the artificial photosynthetic cycle
journal, January 2014
- Yuan, Guangbi; Agiral, Anil; Pellet, Norman
- Faraday Discuss., Vol. 176
Wireless Solar Water Splitting Using Silicon-Based Semiconductors and Earth-Abundant Catalysts
journal, September 2011
- Reece, S. Y.; Hamel, J. A.; Sung, K.
- Science, Vol. 334, Issue 6056
All Inorganic Semiconductor Nanowire Mesh for Direct Solar Water Splitting
journal, November 2014
- Liu, Bin; Wu, Cheng-Hao; Miao, Jianwei
- ACS Nano, Vol. 8, Issue 11
Highly efficient water splitting by a dual-absorber tandem cell
journal, November 2012
- Brillet, Jeremie; Yum, Jun-Ho; Cornuz, Maurin
- Nature Photonics, Vol. 6, Issue 12
Polystyrene sphere-assisted one-dimensional nanostructure arrays: synthesis and applications
journal, January 2011
- Li, Liang; Zhai, Tianyou; Zeng, Haibo
- J. Mater. Chem., Vol. 21, Issue 1
Visible Light-Induced Hole Injection into Rectifying Molecular Wires Anchored on Co 3 O 4 and SiO 2 Nanoparticles
journal, October 2012
- Soo, Han Sen; Agiral, Anil; Bachmeier, Andreas
- Journal of the American Chemical Society, Vol. 134, Issue 41
Roll-to-roll fabrication of large scale and regular arrays of three-dimensional nanospikes for high efficiency and flexible photovoltaics
journal, March 2014
- Leung, Siu-Fung; Gu, Leilei; Zhang, Qianpeng
- Scientific Reports, Vol. 4, Issue 1
Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts
journal, September 2014
- Luo, J.; Im, J. -H.; Mayer, M. T.
- Science, Vol. 345, Issue 6204
Hexagonal nanotubes of ZnS by chemical conversion of monocrystalline ZnO columns
journal, June 2001
- Dloczik, L.; Engelhardt, R.; Ernst, K.
- Applied Physics Letters, Vol. 78, Issue 23
Coupling carbon dioxide reduction with water oxidation in nanoscale photocatalytic assemblies
journal, January 2016
- Kim, Wooyul; McClure, Beth Anne; Edri, Eran
- Chemical Society Reviews, Vol. 45, Issue 11
Multiple nanostructures based on anodized aluminium oxide templates
journal, November 2016
- Wen, Liaoyong; Xu, Rui; Mi, Yan
- Nature Nanotechnology, Vol. 12, Issue 3
A monolithically integrated, intrinsically safe, 10% efficient, solar-driven water-splitting system based on active, stable earth-abundant electrocatalysts in conjunction with tandem III–V light absorbers protected by amorphous TiO 2 films
journal, January 2015
- Verlage, Erik; Hu, Shu; Liu, Rui
- Energy & Environmental Science, Vol. 8, Issue 11
Hollow core–shell nanostructure supercapacitor electrodes: gap matters
journal, January 2012
- Guan, Cao; Xia, Xinhui; Meng, Nan
- Energy & Environmental Science, Vol. 5, Issue 10
Photoelectrochemistry of core–shell tandem junction n–p + -Si/n-WO 3 microwire array photoelectrodes
journal, January 2014
- Shaner, Matthew R.; Fountaine, Katherine T.; Ardo, Shane
- Energy Environ. Sci., Vol. 7, Issue 2
Progress and future directions for atomic layer deposition and ALD-based chemistry
journal, November 2011
- Parsons, Gregory N.; George, Steven M.; Knez, Mato
- MRS Bulletin, Vol. 36, Issue 11
Efficient solar water splitting by enhanced charge separation in a bismuth vanadate-silicon tandem photoelectrode
journal, July 2013
- Abdi, Fatwa F.; Han, Lihao; Smets, Arno H. M.
- Nature Communications, Vol. 4, Issue 1
A Fully Integrated Nanosystem of Semiconductor Nanowires for Direct Solar Water Splitting
journal, May 2013
- Liu, Chong; Tang, Jinyao; Chen, Hao Ming
- Nano Letters, Vol. 13, Issue 6
Conversion of ZnO Nanowires into Nanotubes with Tailored Dimensions
journal, November 2008
- Elias, Jamil; Tena-Zaera, Ramon; Wang, Guillaume-Yangshu
- Chemistry of Materials, Vol. 20, Issue 21
Visible Light Induced Hole Transport from Sensitizer to Co 3 O 4 Water Oxidation Catalyst across Nanoscale Silica Barrier with Embedded Molecular Wires
journal, May 2013
- Agiral, Anil; Soo, Han Sen; Frei, Heinz
- Chemistry of Materials, Vol. 25, Issue 11
Enabling unassisted solar water splitting by iron oxide and silicon
journal, June 2015
- Jang, Ji-Wook; Du, Chun; Ye, Yifan
- Nature Communications, Vol. 6, Issue 1
Efficient photosynthesis of carbon monoxide from CO2 using perovskite photovoltaics
journal, June 2015
- Schreier, Marcel; Curvat, Laura; Giordano, Fabrizio
- Nature Communications, Vol. 6, Issue 1
Charge Transport through Organic Molecular Wires Embedded in Ultrathin Insulating Inorganic Layer
journal, December 2015
- Edri, Eran; Frei, Heinz
- The Journal of Physical Chemistry C, Vol. 119, Issue 51
A Monolithic Photovoltaic-Photoelectrochemical Device for Hydrogen Production via Water Splitting
journal, April 1998
- Khaselev, O.
- Science, Vol. 280, Issue 5362
Direct solar-to-hydrogen conversion via inverted metamorphic multi-junction semiconductor architectures
journal, March 2017
- Young, James L.; Steiner, Myles A.; Döscher, Henning
- Nature Energy, Vol. 2, Issue 4
Formation of nanoscale structures by inductively coupled plasma etching
conference, January 2013
- Welch, Colin C.; Olynick, Deirdre L.; Liu, Zuwei
- International Conference on Micro-and Nano-Electronics 2012, SPIE Proceedings
Sol−Gel Template Synthesis of Semiconductor Oxide Micro- and Nanostructures
journal, November 1997
- Lakshmi, Brinda B.; Patrissi, Charles J.; Martin, Charles R.
- Chemistry of Materials, Vol. 9, Issue 11
Conformal Coating on Ultrahigh-Aspect-Ratio Nanopores of Anodic Alumina by Atomic Layer Deposition
journal, September 2003
- Elam, J. W.; Routkevitch, D.; Mardilovich, P. P.
- Chemistry of Materials, Vol. 15, Issue 18, p. 3507-3517
Ultrafast Charge Transfer between Light Absorber and Co 3 O 4 Water Oxidation Catalyst across Molecular Wires Embedded in Silica Membrane
journal, April 2017
- Edri, Eran; Cooper, Jason K.; Sharp, Ian D.
- Journal of the American Chemical Society, Vol. 139, Issue 15
ZnO Nanotube Based Dye-Sensitized Solar Cells
June 2007
- Martinson, Alex B. F.; Elam, Jeffrey W.; Hupp, Joseph T.
- Nano Letters, Vol. 7, Issue 8, p. 2183-2187
Light Induced Carbon Dioxide Reduction by Water at Binuclear ZrOCo II Unit Coupled to Ir Oxide Nanocluster Catalyst
journal, July 2014
- Kim, Wooyul; Yuan, Guangbi; McClure, Beth Anne
- Journal of the American Chemical Society, Vol. 136, Issue 31
Atomic Layer Deposition of Noble Metals and Their Oxides
journal, September 2013
- Hämäläinen, Jani; Ritala, Mikko; Leskelä, Markku
- Chemistry of Materials, Vol. 26, Issue 1
Comparing Photosynthetic and Photovoltaic Efficiencies and Recognizing the Potential for Improvement
journal, May 2011
- Blankenship, R. E.; Tiede, D. M.; Barber, J.
- Science, Vol. 332, Issue 6031, p. 805-809
Al2O3 Nanotubes Fabricated by Wet Etching of ZnO/Al2O3 Core/Shell Nanofibers
journal, March 2004
- Hwang, J.; Min, B.; Lee, J. S.
- Advanced Materials, Vol. 16, Issue 5
Nano-Photoelectrochemical Cell Arrays with Spatially Isolated Oxidation and Reduction Channels
journal, January 2017
- Park, Hang-Ah; Liu, Siyuan; Oh, Youngseok
- ACS Nano, Vol. 11, Issue 2
Super-selective cryogenic etching for sub-10 nm features
journal, December 2012
- Liu, Zuwei; Wu, Ying; Harteneck, Bruce
- Nanotechnology, Vol. 24, Issue 1
Membranes for artificial photosynthesis
journal, January 2017
- Chabi, Sakineh; Papadantonakis, Kimberly M.; Lewis, Nathan S.
- Energy & Environmental Science, Vol. 10, Issue 6
Hierarchical Inorganic Assemblies for Artificial Photosynthesis
journal, August 2016
- Kim, Wooyul; Edri, Eran; Frei, Heinz
- Accounts of Chemical Research, Vol. 49, Issue 9
In Situ Spectroscopy of Water Oxidation at Ir Oxide Nanocluster Driven by Visible TiOCr Charge-transfer Chromophore in Mesoporous Silica
journal, September 2008
- Han, Hongxian; Frei, Heinz
- The Journal of Physical Chemistry C, Vol. 112, Issue 41
Works referencing / citing this record:
Nanoscale membranes that chemically isolate and electronically wire up the abiotic/biotic interface
journal, June 2018
- Cornejo, Jose A.; Sheng, Hua; Edri, Eran
- Nature Communications, Vol. 9, Issue 1